Abstract
A combination of matrix isolation IR and DFT studies has shown that when monomeric nickel dihalides ( NiX 2, X= Cl, Br ) are condensed in solid nitrogen matrices the initial species formed are NiX 2⋯(N 2) n with a physisorbed type of interaction between the nitrogen and the nickel centre. These can be converted by photolysis into pseudo-tetrahedral NiX 2( η 1-N 2) 2 moieties with end-on bonded dinitrogen ligands in a chemisorbed type of interaction, but only if the matrix is deposited at less than 10 K. On warming to ca. 20 K the chemisorbed species revert to the physisorbed state. For CoBr 2 only very very weak new bands were observed after photolysis in a nitrogen matrix, and no new bands were observed after photolysis for NiF 2, FeBr 2 or ZnBr 2 in nitrogen matrices.
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